Insecticidally active cyano compounds

ABSTRACT

A cyano compound useful as an insecticide, of the formula (I) ##STR1## wherein the radicals are defined in the claims.

This application is a continuation of application Ser. No. 678,382,filed Apr. 1, 1991 now abandoned, which is a division, of applicationSer. No. 584,398 now U.S. Pat. No. 5,066,808, filed Sep. 14, 1990 whichis a continuation application of Ser. No. 419,428, filed Oct. 10, 1989now abandoned.

The present invention relates to novel cyano compounds, to processes fortheir preparation and to their use as insecticides.

It has already been disclosed that certain N-cyanoisothioureas areuseful as medicaments for treating ulcers (see Japanese Patent Laid-openNo. 234,064/1987), and that the N-cyanoisothioureas disclosed in theabove Japanese patent application and other N-cyanoisothioureas havealso a function for controlling insects and plant-destructive nematodes(see Japanese Patent Laid-open No. 233,903/1988 and EP-OS 303,570), andfurthermore that certain N-cyanoguanidines have insecticidal function(see Japanese Patent Laid-open No. 47,766/1989).

There have now been found novel cyano compounds of the formula (I)##STR2## wherein R¹ is hydrogen, cyano or C₁₋₄ alkyl, m is 0 or 1,

R² is hydrogen, C₁₋₆ alkyl, C₃₋₄ alkenyl optionally substituted byhalogen,

C₃₋₄ alkynyl, C₃₋₈ cycloalkyl optionally substituted by methyl,optionally substituted phenyl, optionally substituted benzyl, hydroxy,C₁₋₄ alkoxy or --CH₂ --Z, in which Z has the same meanings as statedbelow,

R³ is --O--R⁴, --S--R⁴ or ##STR3## in which R⁴ is C₁₋₆ alkyl, C₃₋₄alkenyl, C₃₋₄ alkynyl, C₃₋₈ cycloalkyl, optionally substituted phenyl,optionally substituted benzyl or

--(CH₂)n-Z, in which n is 1 or 2 and

Z has the same meanings as stated below, and

R⁵ and R⁶ are hydrogen, C₁₋₉ alkyl optionally substituted by at leastone selected from a group consisting of halogen, hydroxy, mercapto, C₁₋₂alkoxy, C₁₋₂ alkylthio, C₃₋₆ cycloalkyl, amino, C₁₋₂ monoalkylamino,C₂₋₄ (in total)di-alkylamino, carboxy, C₁₋₂ alkoxy-carbonyl and cyano,C₃₋₄ alkenyl optionally substituted by halogen, C₃₋₄ alkynyl, optionallysubstituted phenyl, optionally substituted benzyl, C₁₋₄ alkoxy, hydroxy,formyl, C₁₋₄ alkoxy-carbonyl, C₁₋₄ alkylamino, C₂₋₄ (intotal)di-alkylamino, amino, acyl or ##STR4## in which R¹ and m have thesame meanings as stated above, and Z has the same meanings as statedbelow, and in addition,

R⁵ and R⁶ may form, together with the N-atom to which they are bonded, a3 to 7 membered ring which may be substituted by C₁₋₂ alkyl and maycontain N, O or S as the member of said ring, besides the N-atom towhich they are bonded, and Z is a substituted 5 or 6 memberedheterocyclic group which contains at least one heteroatom selected fromN, O and S as a ring member, provided that where Z is pyridylsubstituted by halogen, m is 1, R² is C₁₋₆ alkyl and R³ is--S-alkyl(C₁₋₆) or --S-benzyl, then R¹ is cyano or C₁₋₄ alkyl.

The compounds of the formula (I) can be obtained when

a) in the case where R³ is --S--R⁴ ; compounds of the formula (II)##STR5## wherein R¹, m, R² and Z have the same meanings as stated above,are reacted with compounds of the formula (III) ##STR6## wherein R⁴ hasthe same meaning as stated above, in the presence of inert solvents, or

b) in the case where R³ is --O--R⁴ ; the aforesaid compounds of theformula (II) are reacted with compounds of the formula (IV) ##STR7##wherein R⁴ has the same meaning as stated above, in the presence ofinert solvents, or

c) in the case where R³ is ##STR8## the aforesaid compounds of theformula (II) are reacted with compounds of the formula (V) ##STR9##wherein R⁴, R⁵ and R⁶ have the same meanings as stated above, in thepresence of inert solvents, or

d) in the case where R³ is --S--R⁴ and m is 1; compounds of the formula(VI) ##STR10## wherein R¹ and Z have the same meanings as stated above,and M is halogen, are reacted with compounds of the formula (VII)##STR11## wherein R² and R⁴ have the same meanings as stated above, inthe presence of inert solvents and if appropriate in the presence of abase.

The novel cyano compounds exhibit powerful insecticidal properties.

Surprisingly, the cyano compounds, according to the invention exhibit asubstantially greater insecticidal function than those known from theaforementioned prior art.

Among the cyano compounds according to the invention, of the formula(I), preferred compounds are those in which

R¹ is hydrogen or C₁₋₃ alkyl,

m is 0 or 1,

R² is hydrogen, C₁₋₄ alkyl, allyl, propargyl, phenyl optionallysubstituted by halogen, benzyloptionally substituted by halogen,hydroxy, C₁₋₃ alkoxy or --CH₂ --Z¹ in which Z¹ is pyridyl optionallysubstituted by halogen,

R³ is --O--R⁴, --S--R⁴ or ##STR12## in which R⁴ is C₁₋₄ alkyl, allyl,propargyl, C₃₋₆ cycloalkyl, phenyl optionally substituted by halogen,benzyl optionally substituted by halogen or --CH₂ --Z¹ in which

Z¹ has the same meaning as stated above,

R⁵ and R⁶ are hydrogen, C₁₋₉ alkyl optionally substituted by fluorine orchlorine, allyl optionally subsutituted by chlorine, propargyl, phenyloptionally substituted by chlorine, benzyl optionally substituted bychlorine, C₁₋₃ alkoxy, hydroxy, hydroxy-C₁₋₂ alkyl, mercapto-C₁₋₂ alkyl,amino-C₁₋₂ alkyl, C₁₋₃ alkylamino, dimethylamino, amino, cyano-C₁₋₂alkyl, pyridyl optionally substituted by chlorine or methyl, or --CH₂--Z² in which Z² is pyridyl optionally substituted by halogen or5-thiazolyl optionally substituted by halogen, and in addition,

R⁵ and R⁶ may form, together with the N-atom to which they are bonded, a3 to 6 membered ring which may be substituted by methyl and may containN, O or S as the member of said ring, besides the N-atom to which theyare bonded, and

Z is a 5 membered heterocyclic group which is substituted by halogen orC₁₋₂ alkyl and contains one or two nitrogen atoms, or one nitrogen atomand either one oxygen atom or one sulfur atom, or a 6 memberedheterocyclic group which is substituted by halogen or C₁₋₂ alkyl andcontains one or two nitrogen atoms, provided that where Z is pyridylsubstituted by halogen, m is 1, R² is C₁₋₄ alkyl and

R³ is --S-alkyl(C₁₋₄) or --S-benzyl, then R¹ is C₁₋₃ alkyl.

Very particularly preferred cyano compounds of the formula (I) are thosein which

R¹ is hydrogen, methyl, ethyl or propyl,

m is 0 or 1

R² is hydrogen, methyl, ethyl, propyl, allyl, propargyl, phenyloptionally substituted by chlorine, hydroxy, methoxy, ethoxy orpyridylmethyl optionally substituted by chlorine,

R³ is --O--R⁴, --S--R⁴ or ##STR13## in which R⁴ is C₁₋₃ alkyl, allyl,propargyl, cyclohexyl, phenyl, benzyl optionally substituted bychlorine, pyridylmethyl optionally substituted by chlorine, R⁵ and R⁶are hydrogen, C₁₋₄ alkyl optionally substituted by fluorine or chlorine,allyl optionally substituted by chlorine, propargyl, phenyl optionallysubstituted by chlorine, benzyl optionally substituted by chlorine,methoxy, hydroxy, hydroxyethyl, C₁₋₂ alkylamino, dimethylamino, amino,cyanoethyl, 2-chloro-5-pyridylmethyl or 2-chloro-5-thiazolylmethyl, andin addition, R⁵ and R⁶ may form, together with the N-atom to which theyare bonded, pyrrolidino, piperidino, 2-methylpiperidino, morpholine,piperazino or isoxazolidino, and Z is a 5 membered heterocyclic groupwhich is substituted by halogen or C₁₋₂ alkyl and contains one or twonitrogen atoms, or one nitrogen atom and either one oxygen atom or onesulfur atom, or a 6 membered heterocyclic group which is substituted byhalogen or C₁₋₂ alkyl and contains one or two nitrogen atoms, providedthat where Z is pyridyl substituted by halogen, m is 1, R² is methyl,ethyl or propyl and R³ is --S-alkyl(C₁₋₃) or --S-benzyl, then

R¹ is methyl, ethyl or propyl.

Specifically, the following compounds may be mentioned:

S-methyl-N-(2-chloro-5-pyridylmethyl)-N'-cyanoisothiourea,

S-methyl-N-(2-chloro-5-thiazolylmethyl)-N'-cyanoisothiourea,

3-(2-chloro-5-pyridylmethyl)-3-methyl-2-cyanoguanidine,

3-(2-chloro-5-pyridylmethyl)-1-methyl-2-cyanoguanidine,

3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-cyanoguanidine,

3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-cyanoguanidine,

3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-cyanoguanidine, and

1,3-bis(2-chloro-5-pyridylmethyl)-2-cyanoguanidine.

If, for example, in the process a), 5-aminomethyl-2-chloropyridine anddimethyl cyanamidodithiocarbonate are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR14##

If, for example, in the process b), 5-aminomethyl-2-chloropyridine anddiethyl cyanamidocarbonate are used as starting materials, the course ofthe reaction can be represented by the following equation: ##STR15##

If, for example, in the process c), 5-aminomethyl-2-chloropyridine and3-cyano-1-methyl-2-methylisothiourea are used as starting materials, thecourse of the reaction can be represented by the following equation:##STR16##

If, for example, in the process d), 2-chloro-5-chloromethylthiazole and3-cyano-2-methylisothiourea are used as starting materials, the courseof the reaction can be represented by the following equation: ##STR17##

In the process a), the compounds of the formula (II) as a startingmaterial mean ones based on the aforementioned definitions of R¹, m, R²and Z.

In the formula (II), R¹, m, R² and Z have preferably the same meaningsas already given above.

The compounds of the formula (II) include known compounds which havebeen described in U.S. Pat. No. 4,499,907 and Nihon Kagaku Zasshi(Periodical of Japanese Chemistry), vol. 83, pp. 218-222, 1962, and asexamples thereof, there may be mentioned:

5-aminomethyl-2-chloropyridine,

5-aminomethyl-2-chlorothiazole and

5-methylaminomethyl-2-chloropyridine.

The compounds of the formula (III), as also a starting material in theprocess a), mean ones based on the aforementioned definition of R⁴.

In the formula (III), R⁴ has preferably the same meaning as alreadygiven above.

The compounds of the formula (III) are known compounds described in forinstance Japanese Patent Publication No. 26,482/1969, and as examples,cyanamidodithio dimethylcarbonate may be exemplified.

In the process b), the compounds of the formula (IV) as a startingmaterial mean ones based on the aforementioned definition of R⁴.

In the process b), R⁴ has preferably the same meaning as already givenabove.

The compounds of the formula (IV) are known compounds described inJapanese Patent Laid-open No. 126,856/1988, and as examples, cyanamidodiethylcarbonate may be exemplified.

In the process c), the compounds of the formula (V) as a startingmaterial mean ones based on the aforementioned definitions of R⁴, R⁵ andR⁶.

In the formula (V), R⁴, R⁵ and R⁶ have preferably the same meanings asalready given above.

The compounds of the formula (V) may be obtained in general when theaforementioned compounds of the formula (III) are reacted with compoundsof the formula (VIII) ##STR18## wherein R⁵ and R⁶ have the same meaningsas stated above, in the presence of inert solvents.

The above compounds of the formula (VIII) are well-known in organicchemistry.

In the process d), the compounds of the formula (VI) as a startingmaterial mean ones based on the aforementioned definitions of R¹, Z andM.

In the formula (VI), R¹ and Z have preferably the same meanings asalready given above, and M preferably represents chlorine or bromine.

The compounds of the formula (VI) are known compounds described inJapanese Patent Laid-open No. 81,382/1987, and as examples, there may bementioned:

2-chloro-5-chloromethylthiazole and

2-chloro-5-chloromethylpyridine.

The compounds of the formula (VII), as also a starting material in theprocess d), mean ones based on the aforementioned definitions of R² andR⁴.

In the formula (VII), R² and R⁴ have preferably the same meanings asalready given above.

The compounds of the formula (VII), in the same way as the above processfor the preparation of the compounds of the formula (V), may be obtainedwhen the aforementioned compounds of the formula (III) are reacted withcompounds of the formula (IX)

    R.sup.2 --NH.sub.2                                         (IX)

wherein R² has the same meaning as stated above, in the presence ofinert solvents,

The above compounds of the formula (IX) are well-known.

Suitable diluents in the process a) are all inert organic solvents.

As examples of such solvents, these preferentially include water;aliphatic, cycloaliphatic and aromatic, optionally chlorinated,hydrocarbons, such as hexane, cyclohexane, petroleum ether, ligroin,benzene, toluene, xylene, methylene chloride, chloroform, carbontetrachloride, ethylene chloride, trichloroethylene, chlorobenzene andthe like; ethers such as diethyl ether, methyl ethyl ether, di-isopropylether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran and thelike; ketones such as acetone, methylethyl ketone, methyl-iso-propylketone, methyl-iso-butyl ketone; nitriles such as acetonitrile,propionitrile, acrylonitrile and the like; alcohols such as methanol,ethanol, iso-propanol, butanol, ethylene glycol and the like; esterssuch as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethyl acetamide and the like; and sulfones and sulfoxidessuch as dimethyl sulfoxide, sulfolane and the like; and bases, forexample, such as pyridine.

The reaction temperature of the process a) can be varied within asubstantial range.

In general, the reaction is carried out at between about 0° and about150° C., preferably between about 20° C. and about 100° C.

The reaction of the process a) can be carried out under normal, elevatedor reduced pressure.

In carrying out the process a), for example, about 1 to 1.2 moles,preferably 1.1 moles of the compounds of the formula (III) may beemployed per mole of the compounds of the formula (II), and thesecompounds are reacted in the presence of inert solvents, for example,alcohol, until the generation of mercaptan has ceased so that thedesired compounds of the formula (I) can be obtained.

In carrying the process b), suitable diluents include the same solventsas exemplified for the process a).

The reaction temperatures of the process b) can be varied within asubstantial range. In general, the reaction is carried out at betweenabout 0° and about 150° C., preferably between 20° C. and about 80° C.

The reaction of the process b) can be carried out under normal, elevatedor reduced pressure.

In carrying out the process b), for example, about 1 to 1.2 moles,preferably about 1 to 1.1 moles of the compounds of the formula (IV) maybe employed per mole of the compounds of the formula (II), and thesecompounds are reacted in the presence of inert solvents, for example,alcohol, so that the desired compounds of the formula (I) can beobtained.

In carrying the process c), suitable diluents include the same solventsas exemplified for the process a).

The reaction temperatures of the process c) can be varied within asubstantial range. In general, the reaction is carried out at betweenabout 0° and about 150° C., preferably between 20° C. and about 100° C.

The reaction of the process c) can be carried out under normal, elevatedor reduced pressure.

In carrying out the process c), for example, about 1 to 1.2 moles,preferably about 1 to 1.1 moles of the compounds of the formula (V) maybe employed per mole of the compounds of the formula (II), and thesecompounds are mixed up during heating, so that the desired compounds ofthe formula (I) can be obtained.

In carrying the process d), suitable diluents include the same solventsas exemplified for the process a), as well as ketones, such as acetone,methylethyl ketone, methylisopropyl ketone, and methyl iso-butyl ketone.

The process d) can be carried out in the presence of a base.

As examples of bases, these preferentially include, for example,potassium hydroxide, sodium hydroxide, sodium hydride, sodium carbonate,potassium carbonate, sodium methoxide, sodium ethoxide, potassiumtert-butoxide, and tert-amines such as triethylamine, diethylaniline,pyridine and the like.

The reaction temperatures of the process d) can be varied within asubstantial range. In general, the reaction is carried out at betweenabout 0 and boiling point of the reaction mixture is preferably betweenabout 0° and about 80° C.

The reaction of the process d) can be carried out under normal, elevatedor reduced pressure.

In carrying out the process d), for example, about 0.8 to 1.2 moles,preferably about 0.9 to 1.1 moles of the compounds of the formula (VII)may be employed per mole of the compounds of the formula (VI), and thesecompounds are reacted in the presence of inert solvents, for example,dimethylsulfoxide, so that the desired compounds of the formula (I) canbe obtained.

The active compounds are well tolerated by plants, have a favorablelevel of toxicity to warm-blooded animals, and can be used for combatingarthropod pests, especially insects which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The above-mentioned pests include:

from the class of the Isopoda, for example Oniscus Asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Diplopoda, for example, Blaniulus guttulatus;

from the class of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.;

from the class of the Symphyla, for example, Scutigerella immaculata;

from the order of the Thysanura, for example, Lepisma saccharina;

from the order of the Collembola, for example, Onychiurus armatus;

from the order of the Orthoptera; for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migrato ria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example, Forficula auricularia;

from the order of the Isoptera, for example, Reticulitermes spp.;

from the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci,

from the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.;

from the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exiqua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana,Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homonamagnanima and Tortrix viridana;

from the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis,Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusssp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica;

from the order of the Hymenoptera for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.;

from the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa;

from the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.;

from the class of the Arachnida, for example, Scorpio maurus andLatrodectus mactans;

from the order of the Aranina, for example Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The plant-parasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaspp., and Trichodorus spp.

Furthermore, in the field of veterinary medicine, the novel compound ofthe present invention can effectively be employed for combating avariety of noxious animal-parasitic pests (internal-andexternal-parasitic pests), e.g., parasitic insects and nemotodes. Suchanimal-parasitic pests may be exemplified as follows:

From the class of Insecta, e.g., Gastrophilus spp., Stomoxys spp.,Tricodectes spp., Rhodnius spp., Ctenocephalides canis and the like.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wet-table powders, suspensions, powders,foams, pastes, granules, aerosols, natural and synthetic materialsimpregnated with active compound, very fine capsules in polymericsubstances, coating compositions for use on seed, and formulations usedwith burning equipment, such as fumigating cartridges, fumigating cansand fumigating coils, as well as ULV cold mist and warm mistformulations.

These formulations may be produced in known manner, for example, bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl napthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example, mineral oilfractions, alcohols, such as butanol or glycol, as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for example,aerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example, alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for example,iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 percent by weight ofactive compound, preferably from 0.5 to 90 percent by weight.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay, as well as a good stability to alkali on limed substrates.

The preparation and use of the active compounds according to theinvention can be seen from the following non-limiting examples.

EXAMPLES OF PREPARATION Example 1 ##STR19##

5-aminomethyl-2-chloropyridine (1.43 g) and cyanamidedithio dimethylcarbonate (1.46 g) were dissolved in methanol (20 ml), while thesolution was refluxed under heating for six hours.

After being allowed to cool, the separated crystals were filtered toobtain the desiredS-methyl-N-(2-chloro-5-pyridylmethyl)-N'-cyanoisothiourea (1.2 g) havinga melting point of from 191° to 194° C.

Example 2 ##STR20##

A mixture of 3-cyano-1-methyl-2-methylisothiourea (0.65 g) and5-aminomethyl-2-chloropyridine (0.72 g) was stirred under heating at100° C. for three hours. Then, the reaction product was cooled to roomtemperature and then purified on silica gel column chromatography(eluent: ethanol/chloroform) to obtain the desired3-(2-chloro-5-pyridylmethyl)-1-methyl-2-cyanoguanidine (0.5 g) having amelting point in the range of from 193° to 197° C.

Example 3 ##STR21##

A mixture of 5-aminomethyl-2-chloropyridine (1.6 g), cyanamide dimethylcarbonate (1.6 g) and ethanol (30 ml) was refluxed under heating forfour hours. Then, under reduced pressure, the ethanol contained in thereaction product was distilled off therefrom, followed by purificationof the residue on silica gel chromatography (eluent: ethanol/chloroform)to obtain the desiredO-ethyl-N-(2-chloro-5-pyridylmethyl)-N'-cyanoisothiourea (1.7 g) havinga melting point in the range of from 161° to 164° C.

Example 4 ##STR22##

To a solution of 3-cyano-2-methylisothiourea (1.0 g) indimethylformamide (30 ml) was portion wise added sodium hydride (0.22 g)at a temperature of from 0° to 5° C., followed by stirring for one hour.Thereafter, 2-chloro-5-chloromethylthiazole (1.5 g) was added to thesolution obtained above at a temperature of from 5° to 10° C., followedby an overnight stirring at room temperature.

After the dimethylformamide contained in the solution had been distilledoff under reduced pressure therefrom, the residue was washed withhexane, water, and chloroform in that order to obtain the desiredS-methyl-N-(2-chloro-5-thiazolylmethyl)-N'-cyano-isothiourea (0.4 g)having a melting point in the range of from 167° to 171° C.

Example 5 ##STR23##

5-Aminomethyl-2-chloropyridine (1.57 g) and cyanamidedithio dimethylcarbonate (1.46 g) were dissolved in methanol (10 ml), while thesolution was refluxed under heating for ten hours.

After being allowed to cool, the ethanol contained therein was distilledoff from the solution and the thus obtained residue was purified onsilica gel column chromatography (eluent: ethanol/chloroform) to obtainthe desiredS,N-dimethyl-N-(2-chloro-5-chloropyridylmethyl)-N'-cyanoisothiourea (1.0g) having n_(D) ²⁰ 1.6212.

Together with the compounds prepared in Example 1 to Example 5, othercompounds that can be obtained in the same way as said Examples areshown in the following Table 1:

                                      TABLE 1                                     __________________________________________________________________________     ##STR24##                                                                    Comp.                                         Physical                        No. Z         R.sup.1                                                                            m R.sup.2    R.sup.3       property                        __________________________________________________________________________         ##STR25##                                                                              H    1 H          SCH.sub.3     mp. 191-194° C.          2                                                                                  ##STR26##                                                                              H    1 H          SCH.sub.3                                     3                                                                                  ##STR27##                                                                              H    1 CH.sub.3   SCH.sub.3                                     4                                                                                  ##STR28##                                                                              H    1 C.sub.2 H.sub.5                                                                          SCH.sub.3                                     5                                                                                  ##STR29##                                                                              H    1 H          SCH.sub.3     mp. 163-166° C.          6                                                                                  ##STR30##                                                                              CH.sub.3                                                                           1 H          SCH.sub.3                                     7                                                                                  ##STR31##                                                                              H    1 CH.sub.3   SCH.sub.3     n.sub.D.sup.20 1.6212           8                                                                                  ##STR32##                                                                              CH.sub.3                                                                           1 H          SCH.sub.3     n.sub.D.sup.20 1.5895 mp.                                                     135-138° C.              9                                                                                  ##STR33##                                                                              H    1                                                                                ##STR34## SCH.sub.3     n.sub.D.sup.20 1.6285           10                                                                                 ##STR35##                                                                              H    1 H          SCH.sub.3     mp. 167-171° C.          11                                                                                 ##STR36##                                                                              H    1 CH.sub.3   SCH.sub.3                                     12                                                                                 ##STR37##                                                                              H    1 H          SCH.sub.3                                     13                                                                                 ##STR38##                                                                              --   0 H          SCH.sub.3     mp. 139-142° C.          14                                                                                 ##STR39##                                                                              H    1 C.sub.2 H.sub.5                                                                          SCH.sub.3                                     15                                                                                 ##STR40##                                                                              H    1 C.sub.3 H.sub.7 -n                                                                       SCH.sub.3                                     16                                                                                 ##STR41##                                                                              H    1 C.sub.3 H.sub.7 -iso                                                                     SCH.sub.3                                     17                                                                                 ##STR42##                                                                              CH.sub.3                                                                           1 C.sub.4 H.sub.9 -n                                                                       SCH.sub.3                                     18                                                                                 ##STR43##                                                                              H    1 CH.sub.2 CCH                                                                             SCH.sub.3     n.sub.D.sup.20 1.6178           19                                                                                 ##STR44##                                                                              H      H          SCH.sub.3                                     20                                                                                 ##STR45##                                                                              H      H          SCH.sub.3                                     21                                                                                 ##STR46##                                                                              H      H          SC.sub.2 H.sub.5                              22                                                                                 ##STR47##                                                                              H      H          SC.sub.2 H.sub.5                                                                            mp. 152-153.5° C.        23                                                                                 ##STR48##                                                                              H      CH.sub.3   SC.sub.2 H.sub.5                              24                                                                                 ##STR49##                                                                              H      H          SC.sub.2 H.sub.5                              25                                                                                 ##STR50##                                                                              --   0 H          SCH.sub.3                                     26                                                                                 ##STR51##                                                                              C.sub.3 H.sub.7 -n                                                                 1 H          SC.sub.2 H.sub.5                              27                                                                                 ##STR52##                                                                              H    1 H          SC.sub.3 H.sub.7 -n                                                                         mp. 141.5-143° C.        28                                                                                 ##STR53##                                                                              H    1 CH.sub.3   SC.sub.3 H.sub.7 -n                           29                                                                                 ##STR54##                                                                              H    1 H          SC.sub.3 H.sub.7 -n                           30                                                                                 ##STR55##                                                                              H    1 H          SC.sub.4 H.sub.9 -n                           31                                                                                 ##STR56##                                                                              H    1 CH.sub.3   SC.sub.4 H.sub.9 -n                           32                                                                                 ##STR57##                                                                              H    1 H          SCH.sub.2 CHCH.sub.2                          33                                                                                 ##STR58##                                                                              H    1 H                                                                                         ##STR59##                                    34                                                                                 ##STR60##                                                                              H    1 CH.sub.3                                                                                  ##STR61##                                    35                                                                                 ##STR62##                                                                              H    1 H                                                                                         ##STR63##                                    36                                                                                 ##STR64##                                                                              CH.sub.3                                                                           1 H                                                                                         ##STR65##                                    37                                                                                 ##STR66##                                                                              C.sub.2 H.sub.5                                                                    1 H          OCH.sub.3                                     38                                                                                 ##STR67##                                                                              H    1 C.sub.2 H.sub.5                                                                          OCH.sub.3                                     39                                                                                 ##STR68##                                                                              H    1 H          OCH.sub.3     mp. 204-207° C.          40                                                                                 ##STR69##                                                                              H    1 CH.sub.3   OCH.sub.3     n.sub.D.sup.20 1.5755           41                                                                                 ##STR70##                                                                              H    1 CH.sub.3   OCH.sub.3                                     42                                                                                 ##STR71##                                                                              H    1 H          OCH.sub.3                                     43                                                                                 ##STR72##                                                                              H    1 C.sub.3 H.sub.7 -n                                                                       OCH.sub.3                                     44                                                                                 ##STR73##                                                                              H    1 H          OC.sub.2 H.sub.5                              45                                                                                 ##STR74##                                                                              H    1 H          OC.sub.2 H.sub.5                              46                                                                                 ##STR75##                                                                              H    1 H          OC.sub.2 H.sub.5                                                                            mp. 161-164° C.          47                                                                                 ##STR76##                                                                              H    1 CH.sub.3   OC.sub.2 H.sub.5                              48                                                                                 ##STR77##                                                                              H    1 H          OC.sub.3 H.sub.7 -n                           49                                                                                 ##STR78##                                                                              H    1 C.sub.2 H.sub.5                                                                           ##STR79##                                    50                                                                                 ##STR80##                                                                              H    1 H                                                                                         ##STR81##                                    51                                                                                 ##STR82##                                                                              H    1 H                                                                                         ##STR83##                                    52                                                                                 ##STR84##                                                                              H    1 CH.sub.3                                                                                  ##STR85##                                    53                                                                                 ##STR86##                                                                              H    1 H                                                                                         ##STR87##                                    54                                                                                 ##STR88##                                                                              H    1 H          NH.sub.2      mp. 142-145° C.          55                                                                                 ##STR89##                                                                              H    1 CH.sub.3   NH.sub.2      mp. 169-173° C.          56                                                                                 ##STR90##                                                                              --   0 H          NH.sub.2                                      57                                                                                 ##STR91##                                                                              H    1 C.sub.3 H.sub.7 -n                                                                       NH.sub.2                                      58                                                                                 ##STR92##                                                                              CH.sub.3                                                                           1 H          NH.sub.2                                      59                                                                                 ##STR93##                                                                              C.sub.4 H.sub.9 -n                                                                 1 H          NH.sub.2                                      60                                                                                 ##STR94##                                                                              H    1 CH.sub.3   NH.sub.2                                      61                                                                                 ##STR95##                                                                              H    1 H          NHCH.sub.3                                    62                                                                                 ##STR96##                                                                              H    1 H          NHCH.sub.3    mp. 193-197° C.          63                                                                                 ##STR97##                                                                              H    1 CH.sub.3   NHCH.sub.3    mp. 113-118° C.          64                                                                                 ##STR98##                                                                              --   0 H          NHCH.sub.3                                    65                                                                                 ##STR99##                                                                              CH.sub.3                                                                           1 CH.sub.3   NHCH.sub.3                                    66                                                                                 ##STR100##                                                                             H    1 H          NHCH.sub.3                                    67                                                                                 ##STR101##                                                                             H    1 CH.sub.3   NHCH.sub.3                                    68                                                                                 ##STR102##                                                                             H    1 H          NHC.sub.2 H.sub.5                             69                                                                                 ##STR103##                                                                             H    1 H          NHC.sub.2 H.sub.5                                                                           mp. 135-137.5° C.        70                                                                                 ##STR104##                                                                             H    1 H          NHC.sub.2 H.sub.5                             71                                                                                 ##STR105##                                                                             H    1 CH.sub.3   NHC.sub.2 H.sub.5                                                                           n.sub.D.sup.20 1.5756           72                                                                                 ##STR106##                                                                             H    1 H          NHC.sub.3 H.sub.7 -n                          73                                                                                 ##STR107##                                                                             H    1 C.sub.4 H.sub.9 -n                                                                       NHC.sub.3 H.sub.7 -n                          74                                                                                 ##STR108##                                                                             H    1 H          NHC.sub.3 H.sub.7 -iso                        75                                                                                 ##STR109##                                                                             H    1 CH.sub.3   NHC.sub.3 H.sub.7 -iso                        76                                                                                 ##STR110##                                                                             H    1 H          NHC.sub.4 H.sub.9 -n                          77                                                                                 ##STR111##                                                                             H    1 CH.sub.3   NHC.sub.4 H.sub.9 -n                          78                                                                                 ##STR112##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 (OCH.sub.3).sub.2         79                                                                                 ##STR113##                                                                             H    1 H          NHCH.sub.2 CF.sub.3                           80                                                                                 ##STR114##                                                                             H    1 CH.sub.3   NHCH.sub.2 CF.sub.3                           81                                                                                 ##STR115##                                                                             H    1 H          NHCH.sub.2 CHCH.sub.2                         82                                                                                 ##STR116##                                                                             H    1 CH.sub.3   NHCH.sub.2 CHCH.sub.2                         83                                                                                 ##STR117##                                                                             H    1 H          NHCH.sub.2 CHCH.sub.2                         84                                                                                 ##STR118##                                                                             H    1 H          NHCH.sub.2 C CH                               85                                                                                 ##STR119##                                                                             H    1 H          NHCH.sub.2 CN                                 86                                                                                 ##STR120##                                                                             H    1 H          NHCH.sub.2 CN                                 87                                                                                 ##STR121##                                                                             H    1 CH.sub.3   NHCH.sub.2 CN                                 88                                                                                 ##STR122##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 CN                        89                                                                                 ##STR123##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 NHCH.sub.3                90                                                                                 ##STR124##                                                                             H    1 CH.sub.3   NHCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2         91                                                                                 ##STR125##                                                                             H    1 CH.sub.3                                                                                  ##STR126##                                   92                                                                                 ##STR127##                                                                             H    1 H                                                                                         ##STR128##                                   93                                                                                 ##STR129##                                                                             H    1 H                                                                                         ##STR130##   mp. 149-153° C.          94                                                                                 ##STR131##                                                                             CH.sub.3                                                                           1 H                                                                                         ##STR132##                                   95                                                                                 ##STR133##                                                                             H    1 CH.sub.3                                                                                  ##STR134##   mp. 123-128° C.          96                                                                                 ##STR135##                                                                             CH.sub.3                                                                           1 CH.sub.3                                                                                  ##STR136##                                   97                                                                                 ##STR137##                                                                             H    1 H                                                                                         ##STR138##   mp. 217-221° C.          98                                                                                 ##STR139##                                                                             H    1 CH.sub.3   N(CH.sub.3).sub.2                             99                                                                                 ##STR140##                                                                             H    1 H          N(CH.sub.3).sub.2                                                                           n.sub.D.sup.20 1.5703           100                                                                                ##STR141##                                                                             --   0 H          N(CH.sub.3).sub.2                             101                                                                                ##STR142##                                                                             H    1 H          N(CH.sub.3).sub.2                             102                                                                                ##STR143##                                                                             H    1 H          N(CH.sub.3).sub.2                             103                                                                                ##STR144##                                                                             H    1 CH.sub.2 CCH                                                                             N(CH.sub.3).sub.2                             104                                                                                ##STR145##                                                                             H    1 H          N(CH.sub.3)C.sub.2 H.sub.5                    105                                                                                ##STR146##                                                                             H    1 H          N(CH.sub.3)C.sub.3 H.sub.7 -n                 106                                                                                ##STR147##                                                                             H    1 CH.sub.3   N(CH.sub.3)CH.sub.2 CHCH                      107                                                                                ##STR148##                                                                             H    1 H          N(CH.sub.3)CH.sub.2 CCH                       108                                                                                ##STR149##                                                                             CH.sub.3                                                                           1 H                                                                                         ##STR150##                                   109                                                                                ##STR151##                                                                             H    1 H                                                                                         ##STR152##                                   110                                                                                ##STR153##                                                                             H    1                                                                                ##STR154##                                                                              N(C.sub.2 H.sub.5).sub.2                      111                                                                                ##STR155##                                                                             H    1 H          N(C.sub.2 H.sub.5).sub.2                      112                                                                                ##STR156##                                                                             --   0 H          N(C.sub.2 H.sub.5).sub.2                      113                                                                                ##STR157##                                                                             H    1 H                                                                                         ##STR158##                                   114                                                                                ##STR159##                                                                             H    1 H                                                                                         ##STR160##                                   115                                                                                ##STR161##                                                                             H    1                                                                                ##STR162##                                                                               ##STR163##                                   116                                                                                ##STR164##                                                                             H    1 H                                                                                         ##STR165##                                   117                                                                                ##STR166##                                                                             H    1 H                                                                                         ##STR167##                                   118                                                                                ##STR168##                                                                             H    1 CH.sub.3                                                                                  ##STR169##                                   119                                                                                ##STR170##                                                                             H    1 H                                                                                         ##STR171##                                   120                                                                                ##STR172##                                                                             H    1 CH.sub.3   NHOCH.sub.3                                   121                                                                                ##STR173##                                                                             H    1 H          NHNH.sub.2                                    122                                                                                ##STR174##                                                                             H    1 CH.sub.3   NHNHCH.sub.3                                  123                                                                                ##STR175##                                                                             H    1 H          NHN(CH.sub.3).sub.2                           124                                                                                ##STR176##                                                                             H    1 CH.sub.3   NHOH                                          125                                                                                ##STR177##                                                                             H    1 H                                                                                         ##STR178##                                   126                                                                                ##STR179##                                                                             H    1                                                                                ##STR180##                                                                              NHCH.sub.3                                    127                                                                                ##STR181##                                                                             CN   1 H          SCH.sub.3                                     128                                                                                ##STR182##                                                                             CN   1 CH.sub.3   SCH.sub.3                                     129                                                                                ##STR183##                                                                             CN   1 H          OCH.sub.3                                     130                                                                                ##STR184##                                                                             CN   1 H          NHCH.sub.3                                    131                                                                                ##STR185##                                                                             H    1 CH.sub.2 CHCHCl                                                                          SCH.sub.3                                     132                                                                                ##STR186##                                                                             H    1 H          NHC.sub.4 H.sub.9 -n                          133                                                                                ##STR187##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 OH                        134                                                                                ##STR188##                                                                             H    1 CH.sub.3   NHCH.sub.2 CH.sub.2 SH                        135                                                                                ##STR189##                                                                             H    1 CH.sub.    NHCH.sub.2 CH.sub.2 NH.sub.2                  136                                                                                ##STR190##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 Cl                        137                                                                                ##STR191##                                                                             H    1 CH.sub.3   NH(CH.sub.2).sub.3 COOH                       138                                                                                ##STR192##                                                                             H    1 H          NHCOOCH.sub.3                                 139                                                                                ##STR193##                                                                             H    1 C.sub.2 H.sub.5                                                                          NHCOOC.sub.2 H.sub.5                          140                                                                                ##STR194##                                                                             H    1 H          SCH.sub.3                                     141                                                                                ##STR195##                                                                             H    1 CH.sub.3   SCH.sub.3                                     142                                                                                ##STR196##                                                                             H    1 H          SCH.sub.3                                     143                                                                                ##STR197##                                                                             H    1 CH.sub.3   SCH.sub.3                                     144                                                                                ##STR198##                                                                             H    1 CH.sub.3   NHC.sub.3 H.sub.7 -n                          145                                                                                ##STR199##                                                                             H    1 H          NHCH.sub.2 CH.sub.2 SCH.sub.3                 146                                                                                ##STR200##                                                                             H    1 H                                                                                         ##STR201##                                   __________________________________________________________________________

Biological Test ##STR202## Example 6

Test on Nephotettix cincticeps having resistance to organophosphorusagents:

Preparation of a test chemical

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether

To form a suitable preparation, 1 part by weight of the active compoundwas mixed with the aforesaid amount of the solvent containing theaforesaid amount of the emulsifier. The mixture was diluted with waterto a predetermined concentration.

Testing method

Onto rice plants, about 10 cm tall, planted in pots each having adiameter of 12 cm was sprayed 10 ml per pot of the water-dilution ofeach active compound in a predetermined concentration prepared as above.The sprayed chemical was dried, and a wire net having a diameter of 7 cmand a height of 14 cm was put over each pot, and 30 female imagoes ofNephotettix cincticeps showing resistance to organophosphorus agentswere released into the net. The pots were each placed in a constanttemperature chamber and the number of dead insects was examined 2 dayslater, and the insect mortality was calculated.

The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                                     Concentration of the                                                                        Insect                                             Compound     active ingredient                                                                           mortality,                                         No.          ppm           %                                                  ______________________________________                                         1           50            100                                                10           50            100                                                62           50            100                                                63           50            100                                                99           50            100                                                Comparative                                                                   E-1          50             0                                                 E-2          50             20                                                ______________________________________                                    

Example 7

Test on planthoppers

Testing method

A water dilution in a predetermined concentration of the active compoundprepared as in Example 6 was sprayed onto rice plants, about 10 cm tall,grown in pots with a diameter of 12 cm in an amount of 10 ml per pot.The sprayed chemical was dried, and a wire net, 7 cm in diameter and 14cm tall, was put over each of the pots. Thirty female imagoes ofMilaparvata lugens Stal of a strain which showed resistance toorganophosphorus chemicals were released into the net. The pots wereleft to stand in a constant temperature chamber and the number of deadinsects was examined two days later. The insect mortality was thencalculated.

In the same way as above, the kill ratio was calculated on Sogatellafurcifera Horvath and organophosphorus-resistant Laodelphax striatellusFallen.

The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Concentration                                                                 of the active   Insect mortality, %                                           Compound                                                                              ingredient  Nilaparvata                                                                             Laodelphax                                                                            Sogatella                               No.     ppm         lugens    striatellus                                                                           furcifera                               ______________________________________                                         1      50          100       100     100                                     62      50          100       100     100                                     63      50          100       100     100                                     99      50          100       100     100                                     Compar-                                                                       ative                                                                         E-1     50           0         0       0                                      E-2     50           0         0       0                                      ______________________________________                                    

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A cyano compound of the formula ##STR203##wherein Z is thiazolyl substituted by halogen, C₁₋₂ -alkyl, or CF₃ R¹ ishydrogen, cyano or C₁₋₄ alkyl, m is 0 or 1, R² is hydrogen, C₁₋₆ alkyl,C₃₋₄ alkenyl unsubstituted or substituted by halogen, C₃₋₄ alkynyl, C₃₋₈cycloalkyl unsubstituted or substituted by methyl, unsubstituted phenylor phenyl substituted by halogen, unsubstituted benzyl or benzylsubstituted by halogen, hydroxy, C₁₋₄ alkoxy or --CH₂ --Z, in which Z isas defined above, R³ is --O--R⁴, --S--R⁴ or ##STR204## in which R⁴ isC₁₋₆ alkyl, C₃₋₄ alkenyl, C₃₋₄ alkynyl, C₃₋₈ cycloalkyl, unsubstitutedphenyl or phenyl substituted by halogen, unsubstituted benzyl or benzylsubstituted by halogen, or --(CH₂)_(n) --Z, in which n is 1 or 2 and Zhas the same meaning as stated above, and R⁵ and R⁶ are hydrogen, C₁₋₉alkyl unsubstituted or substituted by at least one substituent selectedone substituent selected from the group consisting of halogen, hydroxy,mercapto, C₁₋₂ alkoxy, C₁₋₂ alkylthio, C₃₋₆ cycloalkyl, amino, C₁₋₂monoalkylamino, C₂₋₄ (in total) di-alkylamino, carboxy, C₁₋₂alkoxy-carbonyl and cyano, unsubstituted C₃₋₄ alkenyl or C₃₋₄ alkenylsubstituted by halogen, C₃₋₄ alkynyl, unsubstituted phenyl or phenylsubstituted by halogen, unsubstituted benzyl or benzyl substituted byhalogen, C₁₋₄ alkoxy, hydroxy, formyl, C₁₋₄ alkoxycarbonyl, C₁₋₄alkylamino, C₂₋₄ (in total)di-alkylamino, amino or ##STR205## in whichR¹, Z and m have the same meanings as stated above, and in addition, R⁵and R⁶ may form, together with the N atom to which they are bonded, apyrrolidino, piperidino, morpholino, piperazino or isoxazolidino ringwhich is unsubstituted or substituted by C₁₋₂ alkyl.
 2. A cyano compoundof the formula (I) according to claim 1, whereinR¹ is hydrogen or C₁₋₃alkyl, m is 0 or 1 R² is hydrogen, C₁₋₄ alkyl, allyl, propargyl, phenylunsubstituted or substituted by halogen, benzyl unsubstituted orsubstituted by halogen, hydroxy, or C₁₋₃ alkoxy, R³ is --O--R⁴, --S--R⁴or ##STR206## in which R⁴ is C₁₋₄ alkyl, allyl, propargyl, C₃₋₆cycloalkyl, phenyl unsubstituted or substituted by halogen, or benzylunsubstituted or substituted by halogen, R⁵ and R⁶ are hydrogen, C₁₋₉alkyl unsubstituted or substituted by fluorine or chlorine, allylunsubstituted or substituted by chlorine, propargyl, phenylunsubstituted or substituted by chlorine, benzyl unsubstituted orsubstituted by chlorine, C₁₋₃ alkoxy, hydroxy, hydroxy-C₁₋₂ alkyl,mercapto-C₁₋₂ alkyl, amino-C₁₋₂ alkyl, C₁₋₃ alkylamino, dimethylamino,amino, cyano-C₁₋₂ alkyl, or --CH₂ --Z² in which Z² is 5-thiazolylunsubstituted or substituted by halogen, and in addition, R⁵ and R⁶ mayform, together with the N-atom to which they are bonded, a pyrrolidino,piperidino, morpholino, piperazino or isoxazolidino ring which isunsubstituted or substituted by methyl.
 3. A cyano compound of theformula (I) according to claim 1, whereinR¹ is hydrogen, methyl, ethylor propyl, m is 0 or 1 R₂ is hydrogen, methyl, ethyl, propyl, allyl,propargyl, phenyl unsubstituted or substituted by chlorine, hydroxy,methoxy, or ethoxy, R³ is --O--R⁴, --S--R⁴ or ##STR207## in which R⁴ isC₁₋₃ alkyl, allyl, propargyl cyclohexyl, phenyl, or benzyl unsubstitutedor substituted by chlorine, R⁵ and R⁶ are hydrogen, C₁₋₄ alkylunsubstituted or substituted by fluorine or chlorine, allylunsubstituted or substituted by chlorine, propargyl, phenylunsubstituted or substituted by chlorine, benzyl unsubstituted orsubstituted by chlorine, methoxy, hydroxy, hydroxyethyl, C₁₋₂alkylamino, dimethylamino, amino, cyanoethyl, or2-chloro-5-thiazolymethyl, and in addition, R⁵ and R⁶ may form, togetherwith the N-atom to which they are bonded, pyrrolidino, piperidino,2-methylpiperidino, morpholino, piperazino or isoxazolidino.
 4. Acompound according to claim 1, wherein such compoundisS-methyl-N-(2-chloro-5-thiazolylmethyl)-N'-cyanoisothioura of thefollowing formula: ##STR208## orS-methyl-N-(2-chloro-5-thiazolylmethyl)-N'-cyanoisothiourea of thefollowing formula: ##STR209##
 5. An insecticidal composition comprisingan insecticidally effective amount of a cyano compound according toclaim 1 in admixture with a diluent.
 6. A method of combating insectswhich comprises applying to insects or to a habitat of insects aninsecticidally effective amount of a cyano compound according toclaim
 1. 7. A method according to claim 6, wherein said cyano compoundisS-methyl-N-(2-chloro-5-thiazolylmethyl)-N'-cyanoisothiourea.
 8. Acompound according to claim 1, which has the formula: ##STR210##
 9. Themethod according to claim 6, wherein said cyano compound has theformula: ##STR211##